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Chalcogenides of the aminomethylphosphines derived from 1-methylpiperazine, 1-ethylpiperazine and morpholine: NMR, DFT and structural studies for determination of electronic and steric properties of the phosphinesElectronic supplementary information (ESI) available: Crystal packing and short contact pictures, tables and graphs for all discussed correlations, detailed NMR and DFT data, as well as optimized geometries for all presented compounds. CCDC reference numbers 767990-767993. For ESI and c
Chalcogenide derivatives of three aminomethylphosphines: P(CH 2 N(CH 2 CH 2 ) 2 NCH 3 ) 3 ( 1 ), P(CH 2 N(CH 2 CH 2 ) 2 NCH 2 CH 3 ) 3 ( 2 ) and P(CH 2 N(CH 2 CH 2 ) 2 O) 3 ( 3 ) were prepared: oxides - OP(CH 2 N(CH 2 CH 2 ) 2 NCH 3 ) 3 ( 4 ), OP(CH 2 N(CH 2 CH 2 ) 2 NCH 2 CH 3 ) 3 ( 5 ), OP(CH 2 N(...
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| Main Authors: | , , |
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| Format: | Article |
| Language: | English |
| Online Access: | Get full text |
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| Summary: | Chalcogenide derivatives of three aminomethylphosphines: P(CH
2
N(CH
2
CH
2
)
2
NCH
3
)
3
(
1
), P(CH
2
N(CH
2
CH
2
)
2
NCH
2
CH
3
)
3
(
2
) and P(CH
2
N(CH
2
CH
2
)
2
O)
3
(
3
) were prepared: oxides - OP(CH
2
N(CH
2
CH
2
)
2
NCH
3
)
3
(
4
), OP(CH
2
N(CH
2
CH
2
)
2
NCH
2
CH
3
)
3
(
5
), OP(CH
2
N(CH
2
CH
2
)
2
O)
3
(
6
), sulfides - SP(CH
2
N(CH
2
CH
2
)
2
NCH
3
)
3
(
7
), SP(CH
2
N(CH
2
CH
2
)
2
NCH
2
CH
3
)
3
(
8
), SP(CH
2
N(CH
2
CH
2
)
2
O)
3
(
9
) and selenides - SeP(CH
2
N(CH
2
CH
2
)
2
NCH
3
)
3
(
10
), SeP(CH
2
N(CH
2
CH
2
)
2
NCH
2
CH
3
)
3
(
11
), SeP(CH
2
N(CH
2
CH
2
)
2
O)
3
(
12
). The spectroscopic NMR analyses, DFT (B3LYP/6-31G**) calculations together with crystallographic studies of compounds
5
,
6
,
9
and
12
demonstrate that the structures and spectroscopic properties are strongly influenced by the chalcogen atom and not entirely contingent on aliphatic rings in the molecules. TEPs (Tolman's electronic parameters), estimated with DFT methods equal 2059.7 cm
−1
for
1
, 2059.8 cm
−1
for
2
and 2061.2 cm
−1
for
3
. These values are similar to TEPs estimated experimentally for other aminomethylphosphines. Phosphines
1
,
2
and
3
, despite very large Tolman cone angles show rather low influence of molecular geometry on their electronic properties: S4′ (symmetric deformation coordinate) (59.8-64.8) and S4 (63.4-63.7) parameters are moderate. Suresh's steric effect (
S
eff
) parameters for phosphines
1
,
2
and
3
(2.70, 2.73 and 2.66, respectively) indicate minor electron-donating effect. Electronic effect (
E
eff
) parameters (4.92, 5.21 and −0.40, respectively) can be easily modified by changing the substituents.
1
J
(SeP) coupling constants in the selenides are low (
10
: 707.5
11
: 707.5
12
: 709.8 Hz), but do not correlate with the TEP values in a way typical for aliphatic phosphines. The examined compounds do not show mutagenic properties and their potential toxicity is low, which is relevant in the context of their possible medical applications.
The structures and spectroscopic properties of chalcogenide derivatives of P(CH
2
N(CH
2
CH
2
)
2
NCH
3
)
3
, P(CH
2
N(CH
2
CH
2
)
2
NCH
2
CH
3
)
3
and P(CH
2
N(CH
2
CH
2
)
2
O)
3
are strongly influenced by the chalcogen atom. |
|---|---|
| ISSN: | 1477-9226 1477-9234 |
| DOI: | 10.1039/c0dt00037j |